Light-sensitive color-photographic silver halide material

ABSTRACT

A yellow-forming component or color coupler for use in silver halide emulsions in light-sensitive color photography has the general formula   WHEREIN X is a hydrogen atom or a halogen atom; Y is a hydrogen atom, a lower alkoxy group, an aryloxy group or a halogen atom; W is   A HYDROGEN ATOM OR A LOWER ALKOXY GROUP; AND Z is   A HYDROGEN ATOM OR A LOWER ALKOXYCARBONYL GROUP, PROVIDED EITHER ONE OF Z AND W IS ALWAYS   AND BOTH OF THEM CANNOT BE   AT THE SAME TIME. R is an aliphatic hydrocarbon residue having eight to 20 carbon atoms.

United States Patent [72] Inventors Masakuni lwama;

Isaburo lnoue; 'Ieruo Ilanzawa; Kenro Sakamoto; 'lakaya Endo, all of Tokyo, Japan [21] Appl. No. 748,236 [22] Filed July 29, 1968 [45] Patented Oct. 26, 1971 [73] Assignee Konishiroku Photo Industry Co., Ltd. [32] Priority July 27, 1967 [33] Japan [31] 42/47871 [S4] LIGIIT-SENSIT IVE COLOR-PHOTOGRAPIIIC SILVER IIALIDE MATERIAL 8 Claims, No Drawings [52] [1.8. CI 96/100 [51] Int.Cl G034: 1/40 [50] Field of Search 96/ 100 [56] References Cited UNITED STATES PATENTS 3,383,214 5/1968 Anderson 96/100 X 3,458,315 7/1969 Loria 96/562 FOREIGN PATENTS 634,669 9/1964 Belgium 96/100 1,052,488 12/1966 Great Britain Primary ExaminerNorman G. Torchin Assistant Examiner-John L. Goodrow Att0rneysHarry C. Bierman, Jordan B. Bierman and Bierman & Bierman ABSTRACT: A yellow-forming component or color coupler for use in silver halide emulsions in light-sensitive color photography has the general formula I w-Q W X Z wherein X is a hyd rogen atom or a halogen atom; Y is a hydrogen atom, a lower alkoxy group, an aryloxy group or a halogen atom; V 7

a hydrogen atom or a lower alkoxy group; 5552 is :1 hydrogen atom or a 1665? altTJiiycarb onyl group. provided either one of z and w is always C O C H-R CO H:

and both of them cannot be C O C HR cum-cn-co I Hr'co ocmcozm 5 3 omen-cum; lo @cocmcomzGa/ co H. (8) 3 11:

@wocmcomr-Q 15 i C0CH-C1tHn l @cocmcomr co-cn-cuflu N/ \CO H: (in) ct mcococmcomr CO-CH-CrsHn l/ l N l co cn: (u) CO-FH-Cufis: cmococa=coxn--n f \CO(IIH: (12 c-n ca co \N 0011, 49 l 1-00 cocrrcozm can, Ci| r:CH-CO g x--cocncomi coczwoun .v In producing light-sens'tive color-photographic materials by useot'theabove-rnenfionedyelloweouplersofthe present in ventiomanyoftheconventionallyknownproeesesmaybe employed. For example, the yellow coupler of the present in vention is dissolved in a high'boiling solvent having a boiling point above I80 (2., (e4, lrieresyl phosphate, dibutyl phths late,orthelike),orinsmisedsolventthereofvithalowboilingsolvedsuehasbutyl acetate, butyl propionate.orthelike, andthenthesnlutionismisedwithsnaqneousgelatinesolutionoontainingasurfneeactiveagenLSubsequentlyJhesolutionisesnulsifiedhymemsofahigh-speedrotarymixerora ooloidntm'lheresnitisgernulsifiedliquidisdirectlyaddedm atilverlnlideplmp'aphieemulsion,'sappiiedontoamitablewppomsochasafilmhaeorbarytapapenandisthen driedtoremoveamnjorproportionot'thelow-boilingsolvent.

Alternatively, the abovementioned emulsified liquid is once eoldsegfinelyeutandwashedwithwatertoremovethelowhoilinglolvengisaddedtoasilverhalidephotographicemulsion. is applied onto asuitable support as mentioned above andisthendrHInlheabove-mentioned msnnerzthelight- 4 sensitive material of the present invention can-be produced. In the above case, the smountoftheeouplerto'be added to the silver halide photographic emulsion is preferably from l5 to I003. permoleot'silverhalide,hutisnotnecessarily limited to said range.

The thus obtained light-sensitive material is exposed to light, is developed by means of a paraphenylenediamine-type developer and is then bleached, fixed and freed from silver to obtainayellovdyeimagewhichisfsvorableinspectnlsbsotption characteristics and has the maximum absorption around 440m and which-is excellent in transparency and, high in color density. Ftuthermore, since the image is less in deposition ot'the coupler, there is observed neither lightabsorpnon nor stuttering, and the unexposed area is also excellent in Typical developers employed for the development of the lightsensitive photographic materials of the present invention are sulfates, sulfites and hydrochlorides of:

N.Ndiethyl-p-phenylenediamine,

N-ethyl-N-B-rnethanesulfommide-ethyL3-methyl4- aminoaniline,

N-ethyl-N-hydroxyethylp-phenyleuediamine.

N-ethyl-N-hydroxyethyl-2-rnethyl p-phenylenediamine, and

Nfldiethyl-Z-metlryLp-phenylenediamine.

The yellow couplers employed in the present invention are synthesized in the following manner.

A henmyl aoetnnilide derivative having a primary amino group 'scondensed with a longehain alkyl suecinie anhydride. 'lheresultingsuecimnonmide isheatedtogetherwith asulfuric acid-acetic acid mixture and is dehydrated and ringelosed. The reaction product is purified according to a suitable procedure, whereby a high-purity coupler is easily oblained.Further vhenth'sooupleristreatedwithsulfiiryl chloride in an inert solvent. a chlorinesubsn'tuted compound of active methylene is obtained. The long-chain alkyl suecinie anhydride.vrllich isthemaEnsIartingmJter'nL'sdiscIosedin Yulti Kagaku (Grand Organic Chemistry)" Vol. 4, page 366, (published by Asakura Shoten). and is a compound whichhasbeenprodueedonoommercialmalehyuseofa malonicacidcster,along-chainalkylhslideorthelike.

Concrete procwses for synthesizing typical yellow couplers among those exemplified previously which are used in the present invention are shown below.

SYNTHESIS EXAMPLE 1 10 g. of a (3-n-dodecyl suoeinmonoamido benzoyl)- acetanilide (nLp. l63-I64 0. which hs been synthesized from a-(J-aminobenzoyflaeetanilide and l suecinie anhydride.ismixedwithasolutioool'60 rnLotglaeial acetic acid and 6 ml. ofconoentrated sulfuric acid, and the mixture is heated at 70'7$ C. for [0 minutes. Thereafter. the reaction liquid is charged into 500 ml. of water. whereby a white precipitate is formed.

This precipitate is dissolved in 200 ml. of ethyl acetate, and theethylaoetatesolution iswashedvithwatenischnrged with anhydrous sodium sulfate, and is allowed to stand overnight to be dehydrated. When ethyl acetate is removed by distillation, an oily substanceisleft. 'lhisoilysuhstanceisrecrystallized from 100 ml. otaoetonitrile to obtain a white powder (yield 63.5 percent This powder is the coupler exemplified as (I). The elementary analysis values of this coupler are as shown below.

ELEMEXTARY ANALYSIS Percent Calculated Found 1L9. Couple C.) C H N C h N Exempllfiedas(l) 1074M 73. 8 7.99 5.55 73.51 171 527 SYNTHESIS EXAlilPLEB g. of a-( 3-n-octadecyl suecinmonoamido benzoyl)-2- methoxy acetanilide (mp. 169' C.). which has been synthes- S ind from a-(3-aminobenzoyD-2-methoxy aeetanilide and noctadecyl succinic anhydride. is mixed with a Iolution of 540 ml. of glacial acetic acid and 54 ml. of concentrated sulfuric acid, end the mixture is heated at 70-7$ C. for ID minutes.

6 plified as (9) fmm a-benzoyl -noctadecy l succinmonoamido-2-chloroacelanilide. the coupler exemplified as from a-(d-methoxybenmylyi-n-oetadecyl succinmonoamido-Zchloroaeehnilide, and the coupler exemplified Thereafter. the reaction liquid is charged into 4 L. of water, 5 85 from flw y y decyl 91minwhereby a white precipitate is formed. This precipitate is dis- -l-metho ymnilide. solved In bepene. The benzene solution IS with water. m mm: min and mm was values of he recharged wrthmhydmmsodium sulfate, rsallowed tostand wem(7)munmsminmcfouowinshucl overa'qht. when benzene is removed by d'stillation, an oily whetance'sleflfieoilymbaanceisrecrystallizedfromm l0 m l. o[ ethyl to obtain 80 g. of: white powder (yield 92.4 percent). This powder is thecoupler exemplified as (2). BLUENTARY According to the same synthsis process lsabove. there are :2

U n P Calculllzd the coupler exemplified as (3) from -(t-n-hexadecyl suc- Coupk 6; u N c N benmylyl'rnethoxyeeetanilide, "n l 7 7 the coupler exemplified as (4) from a-(3-noctyl succingifimfiglj 31:2 rig 31: 2E

plmed 1. u 7 WWY'HMIWM Ex pllfledg 510)-. 31-32 was in 4.2a was ao 4.30 the coupler exemplified as (5) from a-(3-n-ocudecenyl 2o Exempllficd 501)... 1015-106 7.: w are 1:: n4: 9.27 4.53

succinmononmido benzoyl)-2-chloroacetanilide, and the coupler exemplified as (6) from a-(S-n-octndecyl succinlnonomido benzoy|)-2methoxy 5-ethoxycarbonyl SYNTHESIS EXAMPLE 4 Die 3 points and elementary analysis values of the couplers W u (2) is dmlwd in (z)w(6)mshoninmfmngwez mLolchlorolormTothesolutaon.10.0;ol'mlfurylchlonde is added dropwise at 5l0" C., and the mixture is stirred at l0l$' C. for 2 hours. Therealter. the lolvent is removed by ELEM N NAL under reduced pressure at normal temperature, Percent and the remaining said is recrystallized 2 times from 200 ml. c of ncetonitrile to obtain l0.0 g. of a yellowish-white powder lewd (yield 8 percent). This powder is the coupler exemplified as H N C n N 2 fig 1:23 lnlheserne mannerasabovqthecoupler eremplified as 5;; t: 3g; :5: 1.5: (l3)ts0btmnedfroma-(4-n-octadecylsuccmrmrdobenzoyl)- us am 150 Z-metboxyJ-ethorycnrbonyl acetnmlnde.

SYNTHESIS EXAMPLE 3 4o ELEMENTARY ANALYSIS Pereeut [0.0 g. of a-beuzoyH-n-dodecyl succin mononmido-Z- c M methoxyacetanilide. which has been synthesized from ay. benmy'wmioo-Lmethoxyaeemilidc and n-dodecyl succm C u N Cl C H Cl citric anhydride, is heated at 79-80 C. for 5 minutes together Empuflgd m m fmddm k 'dmd6 l of n :32) 42-43 69.86 3.1 4.29 5.4.1 69.8! 3.4? cu.- 5.15 oenumdsulfurieaiiandthenuiemefion liquidischarged u (n) M ems m: set us out an 3.66 4.62 intommlofntunAaepentedprecipitaeisdisolvedin ethylecetaleendtheethylacetatesclutioniswzshedwith W M 5 the: M with W sulfate. A fll' so Nut in mghb oi bgwggn cou krg hay. wefiyhwwthemnswbdn inglong-chainalkylsuccinimidogroupswhichlreusedinthe from to 5.0 g. of a white pcwder (y 5L3 .present invention and known couplers simihr in structure pereeat). 'lhaspowders the eouplerexemphfieda (7)- thereto are shown in the followin tables: Table l. Com- Aecorringtothe snmeprocesaabovqthereareobtained P l P P f lf a the coupler exemplified a a from ml-s-lhhmcyl (2) s q p y In the m Invention and succnnonoemflo-Z-methoxyaeetnilide. the coupler exerni couple in cm Structural formula M1. C.) lsmnllfied us (3) Cu rCH-c 0 514:

N OCH; CHr-CO COCHrCONB- m7. Cauplsdlsclrxedln U s m 2,:5. CHBGOCmCONHQ 0cm us-m l (can cocmcoml (M disclosed in Jim lum CrtHaCO m rca=cmcom1 TABLE 2 Ccmnlflson In melflng point between the maple: exemplified as (8) among those employed in the unseat lavender: and kno'n couple simlhrln sfl'ucm the'eto Couplg Stmctumflarmuh 3L1. C.) Exmpfified as (8) e OCH; 00- 2 @cocmcorm C O-GH:

Coupk dimlmed In US. Pat. wLlfl. OCH; m4

Asisdeaq'fromtbeabovemblegtheoouplersemployedin creaseincolotdensityofdevelopedcolorimcnsityandi e thepmsentinvemiouuefarlowetinmelfingpointmanthe reductioninamolmlofcouplestobemeAoootdinglyJhe knowncouplemmhencedonotctysallizzinemukionsand light-aemitivephotopzphiemialsoflheprueminvcntion hfihmformedlfletapplicafionlhueoflowppommddryhaveexoellentpbotognphiechanezeristicsinoolonepmducing. ma the couples give stabilized light- 25 mi ai mameliu. sensitive fmt fiik 8106M! wy- The present inventionisifllmzed below with reference to Fmthentatrenzlushovingtheexcdlemsolubifidesofdne emplm w pl sr pmealcoupbsforsolvesmarefllowninlbeu mfi sbynomeanslimileddxereto. blesbelomhachmlheoompuisoninaohbilitywaeffectedbymeauringflielempenmatwhiehlgofooupler mun-El wasdisolvedinZmLofdibutylphthalate. 200g.oflheeouplerexemplifiedas(2)wasaddedma TABLE 8 v 1mm th in the l d 1 Cmnpnrisuninaolubllltybetmtheoouplaexemp ugLamong unemployed presenznvenonlndshn ncouper Wm." Cm SW tmnuh C.) as (2) C|| u-C )6 l C CO cocmcom1- MWIBUB M ,W. 80

* m 20 OCHaCONH ?CH1 .cm, ocmcomz TABLE 4 Comma lnsoluflmy between the mummified as (8km hue In the present Invention and a known couple Similar Dlsolred lemperatm' Coupler Strnctunilamuh C.) u (a) mm @cocn-Coxa CO-CHO I I 131 X 1 CO-(H: 6mm in Us. 1m 2,801,131. gen, :00

As'edwmtieibovemmmmu lmmmixcdsolulioneomptisingZOOmLofdibutylphthalaleand pbyedintbepreseminvendonazeexoeflemakoinaolubilky 600mLofbutylacemteTheresulfingmixmemheatedup for noiveals as oompaxui with the known m80C.!ohavetheoouplercompletelydiaolved.ThiuoIumaple, and hence are markedly useful as pmtected tioawasmixodwithlWmLofalOpemeataquemzseolufign couplers. Moreover, they lave such advantages as the in- 75 of Alkanol BKilkylmphthalene-silfiuatef: at 611m: efl'l L N,N-Diethyl-p-phenylenediamine hydrochloride 2.5 g. Anhydrous sodium sulfite 2.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 20 g. Water to make l,000 ml.

Subsequently, the material was subjected to stopping and fixing treatments according to an ordinary procedure, was washed with water for 10-15 minutes, and was then treated for minutes with a bleaching bath of the following composition:

Potassium ferricyanide 100 g. Potassium bromide 50 g. Water to make t,000 ml.

The material was further washed with water for 5 19 minutes and was fixed for 5 minutes in a fixing bath comprising:

Sodium thiosulfate entahydrate) Water to make 250g. 1,000 ml.

Thereafter, the fixed photographic material was washed with water for 20-25 minutes and was then dried to obtain a brilliant yellow dye image having the maximum absorption at 440 m EXAMPLE 2 100 g. of the coupler exemplified as (8) was added to a mixed solution comprising 100 ml. of tricresyl phosphate and 300 ml. of butyl acetate. The resulting mixture was heated up to 60 C. to have the coupler completely dissolved. This solution was mixed with 50 ml. of a 10 percent aqueous Alkanol B solution and with 2,000 ml. of a 5 percent aqueous gelatine solution, and the mixture was passed through a colloid mill to form a dispersion.

This dispersion was added to 5 kg. of a gelatino silver iodobromide emulsion, which was applied onto a film base and was then dried to obtain a light-sensitive photographic material having a stable light-sensitive layer.

This film was exposed to light and was developed at C. for 10 minutes by means of a developer having the following composition:

Methol 3.0 g. Anhydrous sodium sulfite 60.0 g. Hydroquinone 6.0 g. Anhydrous sodium carbonate 50.0 g. Potassium bromide [.0 g. Water to make L000 ml.

After subjecting to ordinary stopping, hardening treatment and water-washing, the film was again exposed to white light. Subsequently, the film was developed at 20 C. for l2 minutes with a developer of the following composition:

N,N-Diethyl-p-phenylenediarnine hydrochloride 5.0 g. Anhydrous sodium sulfite I Sodium carbonate (monohydrate) 82.0 g. Potassium bromide l .0 g. Water to make 1,000 ml.

Thereafter, the film was subjected to stopping, fixing, waterwashing and bleaching, was washed with running water for 20 minutes, and was then dried to obtain a yellow positive dye image excellent in transparency which had the maximum absorption at 445 mu.

EXAMPLE 3 g. of the coupler exemplified as (12) was mixed with 200 ml. of dibutyl phthalate. The resulting mixtures was heated up to 50 C. to have the coupler completely dissolved. This solution was mixed with 50 ml. of a 10 percent aqueous Alkanol B solution and with 2,000 ml. of a 5 percent aqueous gelatine solution, and the mixture was passed several times through a colloid mill to form a dispersion.

The dispersion was added to 5 kg., of a gelatino silver chlorobromide emulsion, which was applied onto a baryta paper and then dried to obtain a light-sensitive material.

The thus obtained light-sensitive material was exposed to light and was then developed at 20 C. for 10 minutes in a bath of the following composition:

N-Ethyl N-hydroxyethyl-p-phenylenediamine sulfate 2.5 g. Anhydrous sodium sulfite 2.0 g. Hydroxyamine hydrochloride [.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g. Water to make 1,000 rnl.

Subsequently, the developed material was dipped in a stopping bath comprising 10 ml. of glacial acetic acid, 3 .0 g. of caustic soda and 1,000 ml. of water. Immediately thereafter, the treated material was immersed for 4 minutes in an acidic fixing solution. The fixed material was washed with water for l0 minutes, and was then bleached at 20 C. for 8 minutes in a bath of the following composition:

Disodium ethylenediamine tetraacetate 40.0 Ferric chloride 30.0 g. Sodium carbonate (monohydrate) 20.0 g Potassium bromide 30.0 g. Sodium thiosulfate (pentahydrate) 200.0 g. Water to make l 000mlv the thus treated light-sensitive material was washed with water for 20 minutes, was dipped in a stabilizing bath for 2 minutes, and was then dried to obtain a yellow dye image having the maximum absorption at 440 m which was excellent in fastness to light, heat and humidity.

What we claim is:

l. A light-sensitive color-photographic silver halide material characterized by containing a compound represented by the general formula wherein Z is a hydrogen atom or a halogen atom; Y is a hydrogen atom, a lower alkoxy group, an aryloxy group or a halogen atom; W is a hydrogen atom or a lower alkoxy group; and Z is a hydrogen atom or a lower alkoxycarbonyl group, provided either one of Z and W is always CO-GH-R and both of them cannot be CO-OH-R at a same time, where R is an aliphatic hydrocarbon residue having eight to 20 carbon atoms.

2. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula CuHu-CH-C O G /N CHz-CO COCHzCONH (I)CH;

3. A light-sensitive color-photographic silver halide material as claimed in claim I, is wherein said compound is represented by the formula CnHu-CH-C cocmc 0 NH@ 4. A light-sensitive color-photographic silver halide material as claimed in claim I, wherein said compound is represented by the formula CH -CO CH 00 i cocmcoxm (JO 0 C3115 5. A light-sensitive color-photographic silver halide material as claimed in claim I, wherein said compound is represented by the formula OCH;

COCHC1aHsa C 0- H3 6. A light-sensitive color-photographic silver halide material as claimed in claim I, wherein said compound is represented by the formula CO-CH;

7. A light-sensitive color-photographic silver halide material as claimed in claim I, wherein said compound is represented by the formula 8. A light-sensitive color-photographic silver halide material as claimed in claim I, wherein said compound is represented Hy-CO 

2. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula
 3. A light-sensitive color-photograpHic silver halide material as claimed in claim 1, wherein said compound is represented by the formula
 4. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula
 5. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula
 6. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula
 7. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula
 8. A light-sensitive color-photographic silver halide material as claimed in claim 1, wherein said compound is represented by the formula 